Metalized, three-dimensional structured oxygen cathode materials for lithium/air batteries and method for making and using the same

Abstract

This disclosure relates generally to cathode materials for electrochemical energy cells, more particularly to metal/air electrochemical energy cell cathode materials containing silver vanadium oxide and methods of making and using the same. The metal/air electrochemical energy cell can be a lithium/air electrochemical energy cell. Moreover the silver vanadium oxide can be a catalyst for one or more of oxidation and reduction processes of the electrochemical energy cell.

What is claimed is: 
     
       1. An electrode composite material for a metal/air electrochemical energy storage device, the electrode composite comprises M x A y O z  for reducing molecular oxygen, wherein x, y, and z are real positive numbers, M is first metal, A comprises a second metal other than the first metal M and O is oxygen, wherein the second metal A comprises a primary second metal and one or more dopants, wherein the primary second metal comprises vanadium, and wherein the one or more dopants are selected from the group consisting of scandium, titanium, chromium, manganese, iron, cobalt, nickel and copper, wherein the electrode composition material has from about 1 to about 98 wt % M x A y O z . 
     
     
       2. An electrode composite material for a metal/air electrochemical energy storage device, the electrode composite comprises M x A y O z  for reducing molecular oxygen, wherein x, y, and z are real positive numbers, M is first metal, A comprises a second metal other than the first metal M and O is oxygen, wherein the second metal A comprises a primary second metal and one or more dopants, wherein the primary second metal comprises vanadium, wherein the one or more dopants are selected from the group consisting of scandium, titanium, chromium, manganese, iron, cobalt, nickel and copper, and wherein the first metal M further comprises a metal having an atomic number of one of 21-32, 39-42, 44-49, 64, 65, 74-81, or a combination thereof. 
     
     
       3. An electrode composite material for a metal/air electrochemical energy storage device, the electrode composite comprises M x A y O z  for reducing molecular oxygen, wherein x, y, and z are real positive numbers, M is first metal, A comprises a second metal other than the first metal M and O is oxygen, wherein the second metal A comprises a primary second metal and one or more dopants, wherein the primary second metal comprises vanadium, wherein the one or more one dopants are selected from the group consisting of scandium, titanium, chromium, manganese, iron, cobalt, nickel and copper, and wherein the first metal M comprises a M +  cation comprising one of ruthenium, cobalt, rhodium, boron, cerium, europium, erbium, gadolinium, holmium, lithium, lutetium, neodymium, osmium, rhenium, samarium, terbium, iridium, nickel, palladium, platinum, copper, silver, gold, and combinations thereof. 
     
     
       4. An electrode composite material for a metal/air electrochemical energy storage device, the electrode composite comprises M x A y O z  for reducing molecular oxygen, wherein x, y, and z are real positive numbers, M is first metal, A comprises a second metal other than the first metal M and O is oxygen, wherein the second metal A comprises a primary second metal and one or more dopants, and wherein the primary second metal comprises vanadium, and wherein the one or more dopants are selected from the group consisting of scandium, titanium, chromium, manganese, iron, cobalt, nickel and copper, wherein the first metal comprise Cu 2+ . 
     
     
       5. An electrode composite material for a metal/air electrochemical energy storage device, the electrode composite comprises M x A y O z  for reducing molecular oxygen, wherein x, y, and z are real positive numbers, M is first metal, A comprises a second metal other than the first metal M and O is oxygen, wherein the second metal A comprises a primary second metal and one or more dopants, wherein the primary second metal comprises vanadium, and wherein the one or more one dopants are selected from the group consisting of aluminum, antimony, bismuth, chromium, cobalt, copper, cadmium, dysprosium, hafnium, indium, iron, gallium, germanium, lanthanum, molybdenum, manganese, niobium, nickel, praseodymium, rhenium, scandium, silicon, tin, tellurium, titanium, tantalum, tungsten, thallium, thulium, ytterbium, zirconium, zinc, and combinations thereof. 
     
     
       6. The electrode composite material of  claim 1 , wherein one or more of the following are true:
 at least some of the oxygen in the M x A y O z  is replaced with fluoride; 
 (ii) the electrode composition reduces the molecular oxygen to one or more of O 2− , O 2   − , O 2   2− , O 3   − , and O 3   2− ; 
 (iii) the M x A y O z  comprises particulates having an average primary particulate size ranging from about 1 to about 100 μm; 
 (iv) the M x A y O z  has a shape generally resembling a cylindrical rod having a rod length from about 10 to about 200 nm and a rod diameter from about 10 to about 20 nm; 
 (v) the metal/air electrochemical energy storage device comprises a lithium/air battery; and 
 (vi) the M x A y O z  comprises Ag 2 V 4 O 11 . 
 
     
     
       7. The electrode composite material of  claim 2 , wherein one or more of the following are true:
 the electrode composition reduces the molecular oxygen to one or more of O 2− , O 2   − , O 2   2− , O 3   − , and O 3   2− ; 
 (ii) at least some of the oxygen in the M x A y O z  is replaced with fluoride; 
 (iii) the M x A y O z  comprises particulates having an average primary particulate size ranging from about 1 to about 100 μm; 
 (iv) the M x A y O z  has a shape generally resembling a cylindrical rod having a rod length from about 10 to about 200 nm and a rod diameter from about 10 to about 20 nm; 
 (v) the metal/air electrochemical energy storage device comprises a lithium/air battery; and 
 (vi) the M x A y O z  comprises Ag 2 V 4 O 11 . 
 
     
     
       8. The electrode composite material of  claim 4 , wherein one or more of the following are true:
 (i) the M x A y O z  comprises particulates having an average primary particulate size ranging from about 1 to about 100 μm; 
 (ii) at least some of the oxygen in the M x A y O z  is replaced with fluoride; 
 (iii) the electrode composition reduces the molecular oxygen to one or more of O 2− , O 2   − , O 2   2− , O 3   − , and O 3   2− ; 
 (iv) the M x A y O z  has a shape generally resembling a cylindrical rod having a rod length from about 10 to about 200 nm and a rod diameter from about 10 to about 20 nm; 
 (v) the metal/air electrochemical energy storage device comprises a lithium/air battery; and 
 (vi) the M x A y O z  comprises Ag 2 V 4 O 11 . 
 
     
     
       9. The electrode composite material of  claim 5 , wherein one or more of the following are true:
 (i) the M x A y O z  has a shape generally resembling a cylindrical rod having a rod length from about 10 to about 200 nm and a rod diameter from about 10 to about 20 nm; 
 (ii) at least some of the oxygen in the M x A y O z  is replaced with fluoride; 
 (iii) the electrode composition reduces the molecular oxygen to one or more of O 2− , O 2   − , O 2   2− , O 3   − , and O 3   2− ; 
 (iv) the M x A y O z  comprises particulates having an average primary particulate size ranging from about 1 to about 100 μm; 
 (v) the metal/air electrochemical energy storage device comprises a lithium/air battery; and 
 (vi) the M x A y O z  comprises Ag 2 V 4 O 11 . 
 
     
     
       10. An electrode composite material for a metal/air electrochemical energy storage device, the electrode composite comprises M x A y O z  for reducing molecular oxygen, wherein x, y, and z are real positive numbers, M is first metal, A comprises a second metal other than the first metal M and O is oxygen, wherein the second metal A comprises a primary second metal and one or more dopants, wherein the primary second metal comprises vanadium, wherein the one or more dopants are selected from the group consisting of scandium, titanium, chromium, manganese, iron, cobalt, nickel and copper, wherein the electrode composite material further comprises:
 a conductive carbonaceous material; and 
 a polymeric binder, and 
 wherein the M x A y O z  and the conductive carbonaceous material are homogeneously dispersed throughout the polymeric binder. 
 
     
     
       11. The electrode composite material of  claim 10 , wherein the conductive carbonaceous material comprises one of carbon black, activated carbon, graphene sheets, single-walled carbon nano-tubes, multi-walled carbon nanotubes, conductive graphite, carbon fibers and mixtures thereof,
 wherein the polymeric binder comprises one or more of a poly vinylidene fluoride homo-polymer, a poly vinylidene fluoride co-polymer, hexafluoropropylene, a poly vinylidene fluoride-co-hexafluoropropylene, poly(tetrafluoroethylene), styrene-butadiene rubber/sodium carboxyl methyl Cellulose, a modified styrene-butadiene copolymer, and a modified styrene-butadiene aqueous copolymer, wherein the polymeric binder containing the conductive carbonaceous material and the M x A y O z  is in electrical contact with an electrolyte containing an electrolytic salt, and 
 wherein the electrolyte comprises one of dimethlsulfoxide, silanes, tri(ethylene glycol)-substituted trimethylsilane, ethylene carbonate, propylene carbonate, butylene carbonate, ethyl propyl carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, N,N-diethylacetamide, γ-butyrolactone, dimethoxyethane, tetra(ethylene) glycol dimethyl ether, glycol ethers, and tetrahydrofuran, and wherein the electrolytic salt comprises one of lithium perfluorinated alkyl sulfates, lithium perflorinated alkyl ether sulfates, lithium perfluorinated aryl sulfates, lithium perflorinated aryl ether sulfates, lithium perfluorinated alkyl-sulfonates, lithium trifluoromethan sulfonate, lithium perchlorate, lithium bis(oxalato)borate, lithium tetrachloroaluminate, lithium tetrafluoroborate, lithium alkylated borates, lithium B(C 2 H 5 ) 3 C 6 H 13′  lithium tosylate, lithium bis(perfluoroalkylsulfonyl) amide, lithium bis(trifluoromethylsulfonyl)amide, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium bis(pentafluoro ethyl sulfonyl)imide, Lithium tris(trifluoromethylsulfonyl)methide, lithium trifluoro tris(pentafluoroethyl) phosphate, lithium hexafluoroisopropoxide, lithium malonate borate, lithium difluoro(oxalato) borate, and mixtures thereof. 
 
     
     
       12. The electrode composite material of  claim 10 , wherein the conductive carbonaceous material has one or both of a surface area from about 25 to about 2,000 m 2 /g and a pore volume from about 0.1 to about 10 m 3 /g. 
     
     
       13. The electrode composite material of  claim 3 , wherein one or more of the following are true:
 (i) the M x A y O z  comprises Ag 2 V 4 O 11 ; 
 (ii) the electrode composition reduces the molecular oxygen to one or more of O 2− , O 2   − , O 2   2− , O 3   − , and O 3   2− ; 
 (iii) the M x A y O z  comprises particulates having an average primary particulate size ranging from about 1 to about 100 μm; 
 (iv) the M x A y O z  has a shape generally resembling a cylindrical rod having a rod length from about 10 to about 200 nm and a rod diameter from about 10 to about 20 nm; 
 (v) the metal/air electrochemical energy storage device comprises a lithium/air battery; and 
 (vi) at least some of the oxygen in the M x A y O z  is replaced with fluoride. 
 
     
     
       14. A method of using a metal/air electrochemical energy storage device electrode, comprising:
 discharging electrons from an electrode comprising a current collector having an electrode composite material applied to one or more surfaces of the current collector, wherein the electrode composite material comprises a catalyst in the form of M x A y O z  for reducing molecular oxygen, wherein x, y, and z are real positive numbers, M is first metal, A is metal other than M and O is oxygen; and 
 reducing, with the M x A y O z  catalyst and the discharging of the electrons from the electrode, at least some of the molecular oxygen. 
 
     
     
       15. The method of  claim 14 , wherein the catalytic reduction of molecular oxygen reduces the molecular oxygen to one or more of O 2− , O 2   − , O 2   2− , O 3   − , and O 3   2− . 
     
     
       16. The method of  claim 14 , wherein the metal/air electrochemical energy storage device electrode comprises a lithium-containing electrolytic salt and further comprising:
 contacting the catalytically reduced molecular oxygen with the lithium of the lithium-containing electrolytic salt to form Li α O β , where α and β are real, positive numbers. 
 
     
     
       17. The method of  claim 16 , wherein one of following is true:
 the α has a value from about 1 to about 3 and the β has a value from about 1 to about 3; and 
 the α has a value of about 2 and the β has a value of about 1. 
 
     
     
       18. The method of  claim 16 , further comprising:
 applying, after the discharging of the electrons, a charging current to the electrode and wherein the charging current oxidizes the Li x O y  to form molecular oxygen and lithium cations. 
 
     
     
       19. The method of  claim 14 , further comprising:
 reducing, with the discharging of the electrons the electrode at least some, but not most, of the first metal to zero-valent, zero-charge metal particulates. 
 
     
     
       20. The method of  claim 14 , wherein the first metal M comprises one of ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, and combinations thereof, wherein A comprises vanadium and one or more of scandium, titanium, chromium, manganese, iron, cobalt, nickel and copper. 
     
     
       21. The method of  claim 14 , wherein A comprises vanadium. 
     
     
       22. The method of  claim 14 , wherein at least some of the oxygen in the M x A y O z  is replaced with fluoride. 
     
     
       23. The method of  claim 14 , wherein the catalyst has a shaped generally resembling a cylindrical rod having a rod length from about 10 to about 200 nm and a rod diameter from about 10 to about 20 nm. 
     
     
       24. The method of  claim 14 , wherein the metal/air electrochemical energy storage device further comprises:
 a conductive carbonaceous material; 
 a polymeric binder; 
 an electrolyte solvent; and 
 an electrolytic salt, 
 wherein the M x A y O z  and conductive carbonaceous material are homogeneously dispersed throughout the polymeric binder. 
 
     
     
       25. The method of  claim 14 , wherein:
 the conductive carbonaceous material comprises one of carbon black, activated carbon, graphene sheets, single-walled carbon nano-tubes, multi-walled carbon nanotubes, conductive graphite, carbon fibers and mixtures thereof; 
 the polymeric binder comprises one or more of a poly vinylidene fluoride homo-polymer, a poly vinylidene fluoride co-polymer, hexafluoropropylene, a poly vinylidene fluoride-co-hexafluoropropylene, poly(tetrafluoroethylene), styrene-butadiene rubber/sodium carboxyl methyl Cellulose, a modified styrene-butadiene copolymer, and a modified styrene-butadiene aqueous copolymer; 
 the electrolyte comprises one or more of dimethlsulfoxide, silanes, tri(ethylene glycol)-substituted trimethylsilane, ethylene carbonate, propylene carbonate, butylene carbonate, ethyl propyl carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, N,N-diethylacetamide, γ-butyrolactone, dimethoxyethane, tetra(ethylene) glycol dimethyl ether, glycol ethers, and tetrahydrofuran; and 
 the electrolytic salt comprises one of lithium perfluorinated alkyl sulfates, lithium perflorinated alkyl ether sulfates, lithium perfluorinated aryl sulfates, lithium perflorinated aryl ether sulfates, lithium perfluorinated alkyl-sulfonates, lithium trifluoromethan sulfonate, lithium perchlorate, lithium bis(oxalato)borate, lithium tetrachloroaluminate, lithium tetrafluoroborate, lithium alkylated borates, lithium B(C 2 H 5 ) 3 C 6 H 13′  lithium tosylate, lithium bis(perfluoroalkylsulfonyl) amide, lithium bis(trifluoromethylsulfonyl)amide, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium bis(pentafluoro ethylsulfonyl)imide, Lithium tris(trifluoromethylsulfonyl)methide, lithium trifluoro tris(pentafluoroethyl) phosphate, lithium hexafluoroisopropoxide, lithium malonate borate, lithium difluoro(oxalato) borate, and mixtures thereof. 
 
     
     
       26. The method of  claim 14 , wherein M x A y O z  comprise Ag 2 V 4 O 11 . 
     
     
       27. A metal/air electrochemical energy storage device composite electrode, comprising M x A y O z , wherein x, y, and z are real positive numbers, M is first metal, A comprises a second metal other than the first metal M and O is oxygen, wherein the second metal A comprises a primary second metal and one or more dopants, wherein the primary secondary metal comprises vanadium, and wherein the one or more dopants are selected from the group consisting of scandium, titanium, chromium, manganese, iron, cobalt, nickel and copper. 
     
     
       28. The composite electrode of  claim 27 , wherein one or more of the following are true:
 (i) the first metal M comprises a metal having an atomic number of one of 21-32, 39-42, 44-49, 64, 65, 74-81, or combinations thereof; 
 (ii) the electrode composition material has from about 1 to about 98 wt % M x A y O z ; 
 (iii) at least some of the oxygen in the M x A y O z  is replaced with fluoride; 
 (iv) the M x A y O z  comprises particulates having an average primary particulate size ranging from about 1 to about 100 μm; 
 (v) the M x A y O z  has a shaped generally resembling a cylindrical rod having a rod length from about 10 to about 200 nm and a rod diameter from about 10 to about 20 nm; 
 (vi) the metal/air electrochemical energy storage device comprises a lithium/air battery; and 
 (vii) M x A y O z  comprises Ag 2 V 4 O 11 . 
 
     
     
       29. A metal/air electrochemical energy storage device composite electrode, comprising M x A y O z , wherein x, y, and z are real positive numbers, M is first metal, A comprises a second metal other than the first metal M and O is oxygen, wherein the first metal comprise Cu 2+ . 
     
     
       30. The composite electrode of  claim 29 , wherein one or more of the following are true:
 (i) the second metal A comprises an element selected from the group consisting of the elements contained in Groups 3-7, Groups 8-14 of the periodic table of elements and Re; 
 (ii) the electrode composition material has from about 1 to about 98 wt % M x A y O z ; 
 (iii) the second metal A is metal other than manganese; 
 (iv) the second metal A comprises vanadium; 
 (v) at least some of the oxygen in the M x A y O z  is replaced with fluoride; 
 (vi) the M x A y O z  comprises particulates having an average primary particulate size ranging from about 1 to about 100 μm; 
 (vii) the M x A y O z  has a shaped generally resembling a cylindrical rod having a rod length from about 10 to about 200 nm and a rod diameter from about 10 to about 20 nm; 
 (viii) the metal/air electrochemical energy storage device comprises a lithium/air battery; and 
 (ix) M x A y O z  comprises Ag 2 V 4 O 11 . 
 
     
     
       31. A metal/air electrochemical energy storage device composite electrode, comprising M x A y O z , wherein x, y, and z are real positive numbers, M is first metal, A comprises a second metal other than the first metal M and O is oxygen, further comprising:
 a conductive carbonaceous material; and 
 a polymeric binder, 
 wherein the M x A y O z  and the conductive carbonaceous material are homogeneously dispersed throughout the polymeric binder. 
 
     
     
       32. The composite electrode of  claim 31 , wherein the conductive carbonaceous material comprises one of carbon black, activated carbon, graphene sheets, single-walled carbon nano-tubes, multi-walled carbon nanotubes, conductive graphite, carbon fibers and mixtures thereof,
 wherein the polymeric binder comprises one or more of a poly vinylidene fluoride homo-polymer, a poly vinylidene fluoride co-polymer, hexafluoropropylene, a poly vinylidene fluoride-co-hexafluoropropylene, poly(tetrafluoroethylene), styrene-butadiene rubber/sodium carboxyl methyl Cellulose, a modified styrene-butadiene copolymer, and a modified styrene-butadiene aqueous copolymer, 
 wherein the polymeric binder containing the conductive carbonaceous material and the M x A y O z  are in electrical contact with an electrolyte containing an electrolytic salt, and 
 wherein the electrolyte comprises one of dimethlsulfoxide, silanes, tri(ethylene glycol)-substituted trimethylsilane, ethylene carbonate, propylene carbonate, butylene carbonate, ethyl propyl carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, N,N-diethylacetamide, γ-butyrolactone, dimethoxyethane, tetra(ethylene) glycol dimethyl ether, glycol ethers, and tetrahydrofuran, and wherein the electrolytic salt comprises one of lithium perfluorinated alkyl sulfates, lithium perflorinated alkyl ether sulfates, lithium perfluorinated aryl sulfates, lithium perflorinated aryl ether sulfates, lithium perfluorinated alkyl-sulfonates, lithium trifluoromethan sulfonate, lithium perchlorate, lithium bis(oxalato)borate, lithium tetrachloroaluminate, lithium tetrafluoroborate, lithium alkylated borates, lithium B(C 2 H 5 ) 3 C 6 H 13′  lithium tosylate, lithium bis(perfluoroalkylsulfonyl) amide, lithium bis(trifluoromethylsulfonyl)amide, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium bis(pentafluoro ethyl sulfonyl)imide, Lithium tris(trifluoromethylsulfonyl)methide, lithium trifluoro tris(pentafluoroethyl) phosphate, lithium hexafluoroisopropoxide, lithium malonate borate, lithium difluoro(oxalato) borate, and mixtures thereof. 
 
     
     
       33. The composite electrode of  claim 31 , wherein the conductive carbonaceous material has one or both of a surface area from about 25 to about 2,000 m 2 /g and a pore volume from about 0.1 to about 10 m 3 /g.